CN105873716A - Cu core ball, solder paste, formed solder, cu core column, and solder joint - Google Patents

Cu core ball, solder paste, formed solder, cu core column, and solder joint Download PDF

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Publication number
CN105873716A
CN105873716A CN201480072248.7A CN201480072248A CN105873716A CN 105873716 A CN105873716 A CN 105873716A CN 201480072248 A CN201480072248 A CN 201480072248A CN 105873716 A CN105873716 A CN 105873716A
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China
Prior art keywords
ball
solder
core
core ball
layer
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Granted
Application number
CN201480072248.7A
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Chinese (zh)
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CN105873716B (en
Inventor
服部贵洋
相马大辅
六本木贵弘
佐藤勇
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
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    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0218—Composite particles, i.e. first metal coated with second metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process

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Abstract

Provided are a Cu core ball and a Cu core column making it possible to obtain drop strength and strength in relation to heat cycle. The Cu core ball (1) is provided with: a Cu ball (2) configured from Cu or a Cu alloy; and a solder layer (3) configured from a solder alloy comprising Sn and Cu, the solder layer (3) covering the Cu ball (2). The solder layer (3) contains 0.1-3.0% Cu, the balance being Sn and unavoidable impurities.

Description

Cu core ball, soldering paste, shaping solder, Cu stem stem and soldered fitting
Technical field
The present invention relates to solder alloy cover Cu ball Cu core ball, use Cu core ball soldering paste, Use shaping solder, the use soldered fitting of Cu core ball, Cu stem stem (column) and making of Cu core ball Soldered fitting with Cu stem stem.
Background technology
In recent years, due to the prosperity of small information equipment, the electronic unit carried is just at Rapid miniaturization. Electronic unit according to the requirement of miniaturization, connects narrowization of terminal, the reducing of erection space to tackle Change, applying the BGA Package (hereinafter referred to as " BGA ") being provided with electrode overleaf.
Utilize in the electronic unit of BGA, such as, have semiconductor package body.In semiconductor package body, have The semiconductor chip of electrode is sealed by resin.It is formed with solder projection on the electrode of semiconductor chip.This weldering Material projection is by making soft solder to be made the solder ball of spherical gained, soft solder is made the weldering of column gained Stock column is engaged in the electrode of semiconductor chip and is formed.The semiconductor package body utilizing BGA is convex with each solder Block is placed on printed base plate with the mode of the electric conductivity contact pads of printed base plate, utilizes heating to melt Solder projection engage with pad, thus be equipped on printed base plate.It addition, in order to tackle further The requirement of high-density installation, is studying three-dimensional high semiconductor package body stacked along short transverse Density is installed.
But, when applying BGA in having carried out the semiconductor package body that three-dimensional high-density is installed, due to half The deadweight of conductor packaging body, solder ball is crushed, can occur to connect short circuit between electrode.This carry out highly dense Degree is installed and is become obstacle.
Therefore, have studied and utilize such as Cu core ball, the solder projection of Cu stem stem, described Cu core ball, Cu The ball of minute diameter, the cylinder of column that metal high for fusing point by Cu geometric ratio soft solder is formed by stem stem are made It is coated with soft solder for core and on its surface.About having the solder projection of Cu ball etc., by electronic unit When being installed on printed base plate, even if the weight of semiconductor package body puts on solder projection, it is also possible to utilize Cu ball not melted under the fusing point of solder supports semiconductor package body.Therefore, will not be because of semiconductor packages The deadweight of body and make solder projection crushed.As the correlation technique of Cu core ball, include, for example out patent Document 1.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-99736 publication
Summary of the invention
The problem that invention is to be solved
Additionally, for the solder projection using solder ball, solder post, Cu core ball or Cu stem stem to make, Require to have and wait the intensity impacted and for being caused by the variations in temperature being referred to as thermal cycle for falling Flexible intensity.
In the solder ball made of the solder alloy containing Ag, drop strength, strong for thermal cycle Degree all can obtain the intensity of regulation.In order to reduce the cost of solder alloy, even making the addition of Ag Be the solder alloy being referred to as low Ag of about 1.0%, drop strength, for thermal cycle intensity also All can obtain the intensity of regulation.
On the other hand, in the solder ball made of the solder alloy not containing Ag, although drop strength The intensity of regulation can be obtained, but observe the reduction of the intensity for thermal cycle.
The problem of the present invention is, makes Cu core ball also can obtain and solder ball or above on an equal basis the falling of solder post Lower intensity and the intensity for thermal cycle, it is provided that such Cu core ball, the use soldering paste of Cu core ball, one-tenth Shape solder, soldered fitting, Cu stem stem, the soldered fitting of use Cu stem stem.
For solving the scheme of problem
The present inventor etc. find: cover the Cu core ball of Cu ball, with or not the solder alloy not containing Ag Solder alloy containing Ag covers the Cu stem stem of Cu post and makes with using the solder alloy not containing Ag Solder ball or solder post are compared, and drop strength is phase same level, and the intensity for thermal cycle improves.
Therefore, the present invention is as follows.
(1) a kind of Cu core ball, it possesses: the core being made up of Cu or the Cu alloy containing more than 50% Cu Layer；It is made up of and covers the solder layer of sandwich layer the solder alloy comprising Sn and Cu.
(2) according to the Cu core ball described in above-mentioned (1), wherein, solder layer contains more than 0.1% and 3.0% Cu, surplus is made up of Sn and impurity.
(3) according to the Cu core ball described in above-mentioned (2), wherein, with comprising a kind in Ni and Co The covered above-mentioned sandwich layer of layer of above element is covered by above-mentioned solder layer.
(4) according to the Cu core ball described in above-mentioned (3), wherein, alpha ray amount is 0.0200cph/cm2With Under.
(5) a kind of soldering paste, the Cu core ball according to any one of its use above-mentioned (1)～above-mentioned (4).
(6) a kind of shaping solder, the Cu according to any one of its use above-mentioned (1)～above-mentioned (4) Core ball.
(7) a kind of soldered fitting, the Cu according to any one of its use above-mentioned (1)～above-mentioned (4) Core ball.
(8) a kind of Cu stem stem, it possesses: the core being made up of Cu or the Cu alloy containing more than 50% Cu Layer: be made up of and cover the solder layer of sandwich layer the solder alloy comprising Sn and Cu.
(9) according to the Cu stem stem described in above-mentioned (8), wherein, solder layer contains more than 0.1% and 3.0% Following Cu, surplus is made up of Sn and impurity.
(10) according to the Cu stem stem described in above-mentioned (9), wherein, with comprising 1 in Ni and Co The covered sandwich layer of layer planting above element is covered by solder layer.
(11) according to the Cu stem stem described in above-mentioned (10), wherein, alpha ray amount is 0.0200cph/cm2 Below.
(12) a kind of soldered fitting, the Cu according to any one of its use above-mentioned (8)～above-mentioned (11) Stem stem.
The effect of invention
In the present invention, drop strength, intensity for thermal cycle all can obtain required prescribed strength. The solder ball made of the solder alloy not containing Ag and the weldering made of the solder alloy containing Ag Pellet is compared, and the intensity for thermal cycle reduces, but in the present invention, and with the solder alloy containing Ag The Cu core ball made is compared, and can not only obtain required drop strength, and for the intensity of thermal cycle Also can improve.Cu stem stem too, with containing Ag solder alloy make Cu stem stem compared with, Required drop strength can not only be obtained, and the intensity for thermal cycle also can improve.
Accompanying drawing explanation
Fig. 1 is the sectional view of the schematic structure of the Cu core ball illustrating present embodiment.
Fig. 2 is the side cross-sectional, view of the schematic structure of the Cu stem stem illustrating present embodiment.
Fig. 3 is the top cross-sectional view of the schematic structure of the Cu stem stem illustrating present embodiment.
Detailed description of the invention
It is described more particularly below the situation applying the present invention to Cu core ball.In this manual, about The unit (ppm, ppb and %) of the composition of Cu core ball represents phase in the case of not specifying Ratio (quality ppm, quality ppb and quality %) for quality.
Fig. 1 is the sectional view of the schematic structure of the Cu core ball illustrating present embodiment.Present embodiment Cu core ball 1 is made up of the solder layer 3 of Cu ball 2 and covering Cu ball.
Solder layer 3 is more than 0.1% and less than 3.0% by the addition making Cu, is made surplus be not containing of Sn The solder alloy of Ag is constituted, and forms solder layer 3 by carrying out soft solder plating on the surface of Cu ball 2. Cu ball 2 is made up of Cu or the Cu alloy containing more than 50% Cu.
Cu core ball 1 is formed with barrier layer 4 between Cu ball 2 and solder layer 3.Barrier layer 4 is by selected from Ni Or more than a kind element in Co etc. is constituted, prevent the Cu constituting Cu ball 2 from diffusing to solder layer 3.
For utilizing on the surface of Cu ball 2, to make the addition of Cu be more than 0.1% and less than 3.0%, it is remaining to make For the solder alloy that amount is the composition not containing Ag of Sn is formed with the Cu core ball 1 of solder layer 3, i.e. Making coalesced object thing is to implement the Cu-OSP substrate of pre-solder flux process on the surface of Cu layer, at Cu layer Surface implement the electroplated Ni/Au substrate of electroplated Ni/Au, for impacts such as falling intensity and for It is strong that the flexible intensity caused by the variations in temperature being referred to as thermal cycle the most all can obtain required regulation Degree.
The solder ball made of the solder alloy not containing Ag makes with of the solder alloy containing Ag Solder ball compare, for thermal cycle intensity reduce.Cu core ball 1 for present embodiment, although Solder layer 3 is to be formed by the solder alloy not containing Ag, but with the solder alloy containing Ag The Cu core ball made is compared, and can not only obtain required drop strength, and for the intensity of thermal cycle Also can improve.
For utilizing the solder projection of Cu core ball 1, even if to put on solder convex for the weight of semiconductor package body Block, it is also possible to utilize Cu ball not melted under the fusing point of solder alloy to support semiconductor package body.Cause This, will make solder projection crushed because of the deadweight of semiconductor package body.
Additionally, the miniaturization of electronic unit makes high-density installation be possibly realized, but high-density installation can cause The problem of soft error.Soft error refers to that there is alpha ray enters into semiconductor integrated circuit (hereinafter referred to as " IC ") memory element in thus rewrite storage content probability.
Alpha ray be considered as the U by containing as impurity in solder alloy, Th,210Po etc. are put Injectivity isotope generation alpha-decay and radiate.Therefore, carried out realizing the soft pricker of low Alpha-ray composition The exploitation of material alloy.
In Cu core ball 1, Cu ball 2 is covered by solder layer 3, if thus constituting the solder alloy of solder layer 3 Low alpha ray can be realized, then it is assumed that the alpha ray radiated from Cu ball 2 can be covered, but for Cu ball 2, Also require that by realizing low Alpha-ray form.
And then, in Cu core ball 1, if representing relatively low, then in shape close to the sphericity of ball with which kind of degree When becoming solder projection, mobility and the uniformity of soft solder amount during installation reduce.Therefore, it is desirable to The Cu core ball 1 that sphericity is high.
Solder layer 3 consist of the Lead-free solder alloy using Sn as main component, from for falling Impact intensity and for the intensity of thermal cycle from the viewpoint of, for Sn-Cu alloy.Cu core ball 1 In, the thickness of solder layer 3 is not particularly limited, preferably 100 μm (unilateral) are below the most enough. Usually 1～50 μm.
Solder layer 3 makes Cu ball 2, flow of the electrolyte be formed.Utilize the flowing of plating solution, in the plating solution Pb, Bi, Po element forms salt and precipitates.Once form the precipitate as salt, will the most stably deposit ?.Accordingly, with respect to the Cu core ball 1 of the present invention, precipitate will not be introduced in solder layer 3, it is possible to fall The content of radioelement contained in low solder layer 3, the alpha ray amount of minimizing Cu core ball 1 self becomes can Energy.
Hereinafter, the composition that can realize low Alpha-ray solder layer 3 is described in detail.
Below U:5ppb, below Th:5ppb
U and Th is radioelement, in order to suppress soft error, needs to suppress their content.In order to incite somebody to action The alpha ray amount of solder layer 3 is set to 0.0200cph/cm2Hereinafter, the content making U and Th is needed to be respectively 5ppb Below.Additionally, from the viewpoint of suppression soft error now or high-density installation in the future, U and The content of Th is preferably respectively below 2ppb.
Alpha ray amount: 0.0200cph/cm2Below
The alpha ray amount of the Cu core ball 1 of the present invention is 0.0200cph/cm2Below.This is the height at electronic unit In density installation, soft error will not become the alpha ray amount of the level of problem.The α of the Cu core ball 1 of the present invention penetrates Line amount can be 0.0200cph/cm by constituting the alpha ray amount of the solder layer 3 of Cu core ball 12Hereinafter realize. Additionally, the alpha ray amount of Cu core ball 1 is as be described hereinafter, it is possible to be 0.0200cph/cm by the alpha ray amount of Cu ball 22 Hereinafter realize.
The Cu core ball 1 of the present invention is formed at not higher than 100 DEG C, be therefore difficult to the imagination utilize U, Th,210The gasification of the radioelement of Po, Bi and Pb etc. and make the content of radioelement reduce.But, limit Make plating solution, Cu ball 2 limit of flowing when carrying out plating, U, Th, Pb, Bi and210Po can be formed in the plating solution Salt also precipitates.The salt of precipitation is electric neutrality, even if flow of the electrolyte, also will not be mixed into soft solder plating film In.
Therefore, their content in soft solder plating film significantly reduces.Therefore, the Cu core ball of the present invention 1 shows low alpha ray amount owing to being covered by this solder layer 3.Alpha ray amount is highly the densest from suppression From the viewpoint of soft error in degree installation, preferably 0.0020cph/cm2Below, more preferably 0.0010cph/cm2Below.
The purity of the solder layer 3 constituting the Cu core ball 1 of the present invention is the highest, i.e. the content of impurity in solder layer 3 The fewest, then the content of radioelement more reduces, and alpha ray amount more reduces, the therefore lower limit to impurity level Value is not particularly limited.On the other hand, from the viewpoint of reducing alpha ray amount, higher limit is preferably Below 1000ppm, more preferably below 100ppm, more preferably below 50ppm, particularly preferably For below 10ppm.
It should be noted that the total impurities amount of solder layer 3 is miscellaneous in addition to Sn and Cu in solder layer 3 The summation of the content of matter.
In impurity contained in solder layer 3, the content of particularly preferred Bi and Pb is few.Bi and Pb wraps respectively Radioactivity peer containing trace210Bi and210Pb.It is understood that by the content reducing Bi and Pb, The alpha ray amount of solder layer 3 can be significantly reduced.The content of Bi and Pb in solder layer 3 is preferably respectively Below 15ppm, more preferably respectively below 10ppm, particularly preferably respectively 0ppm.
Then, the composition composition of Cu ball 2 of Cu core ball 1 of the present invention, alpha ray amount, sphericity are carried out Describe in detail.
For constituting the Cu ball 2 of the Cu core ball 1 of the present invention, when Cu core ball 1 is for solder projection, soft Will not melt at a temperature of soldering, therefore, it can suppress the highly non-uniform of soldered fitting.Therefore, excellent Choosing, the sphericity of Cu ball 2 is high, diameter uneven few.Additionally, as it was previously stated, preferred Cu ball The alpha ray amount of 2 is also low in the same manner as solder layer 3.Hereinafter, the preferred version of Cu ball 2 is recorded.
Below U:5ppb, below Th:5ppb
As it was previously stated, U and Th is radiosiotope, in order to suppress soft error, need to suppress theirs Content.In order to the alpha ray amount of Cu ball 2 is set to 0.0200cph/cm2Hereinafter, need to make the content of U and Th It is respectively below 5ppb.Additionally, from the viewpoint of suppression soft error now or high-density installation in the future Setting out, the content of U and Th is preferably respectively below 2ppb.
The purity of Cu ball: more than 99.9% and less than 99.995%
The purity of Cu ball 2 is more than 3N and below 4N5.It is to say, the content of the impurity element of Cu ball 2 For more than 50ppm.Herein, about the purity of the metal materials such as Cu, it is denoted as 2N by 99%, by 99.9% It is denoted as 3N, is denoted as 4N by 99.99%, be denoted as 5N by 99.999%.4N5 represents that the purity of metal material is 99.995%.
When the purity of the Cu constituting Cu ball 2 is this scope, it is possible to guarantee in melted Cu for making Cu ball 2 Sphericity improve an adequate amount of nucleus.The reason that sphericity improves is following detailed description.
When manufacturing Cu ball, be formed as the Cu material use heating of the small pieces of regulation shape and melt, melted Cu becomes spherical because of surface tension, and it occurs solidification to form Cu ball 2.Melted Cu coagulates from liquid condition Gu during, crystal grain grows in spherical melted Cu.Now, if impurity element is many, then this impurity Element becomes nucleus, the growth of suppression crystal grain.Therefore, spherical melted Cu utilizes growth to be suppressed Fine-grain and form the Cu ball 2 that sphericity is high.
On the other hand, if impurity element is few, the impurity element the most correspondingly becoming nucleus is few, grain growth Will not be suppressed, but grow while there is certain directivity.Its result, the surface of spherical melted Cu A part can highlight and solidify.The sphericity of this Cu ball is low.As impurity element, it may be considered that Sn, Sb, Bi, Zn, Fe, Al, As, Ag, In, Cd, Cu, Pb, Au, P, S, U, Th etc..
The lower limit of purity is not particularly limited, and from suppression alpha ray amount, suppression is led by the reduction of purity From the viewpoint of the deterioration of the electrical conductivity of Cu ball 2 of cause, thermal conductivity, preferably more than 3N.It is to say, The content of the impurity element being preferably the Cu ball 2 in addition to Cu is less than 1000ppm.
Alpha ray amount: 0.0200cph/cm2Below
The alpha ray amount of Cu ball 2 is 0.0200cph/cm2Below.This is in the high-density installation of electronic unit Soft error will not become the alpha ray amount of the level of problem.In the present invention, except leading to manufacture Cu ball 2 Outside the operation often carried out, also it is again carried out heat treated.Therefore, minimal residue in Cu material210Po Volatilization, compared with Cu material, Cu ball 2 shows lower alpha ray amount.Highly the densest from suppression From the viewpoint of soft error in degree installation, alpha ray amount is preferably 0.0020cph/cm2Below, more preferably For 0.0010cph/cm2Below.
In Pb or Bi, the content of any one or the total content of Pb and Bi are more than 1ppm
As impurity element contained in Cu ball 2, it may be considered that Sn, Sb, Bi, Zn, Fe, Al, As, Ag, In, Cd, Cu, Pb, Au, P, S, U, Th etc., but, for constituting the Cu of the present invention The Cu ball 2 of core ball 1, in the middle of impurity element, particularly preferably with any one content in Pb or Bi or Pb Contain as impurity element with the mode that total content is more than 1ppm of Bi.In the present invention, penetrate from reducing α The aspect of line amount is set out, it is not necessary that the content of any one in Pb or Bi or the content of Pb and Bi are subtracted Few to the limit.
This is because following reason.
210Pb is decayed by β and is changed into210Bi,210Bi is decayed by β and is changed into210Po,210Po passes through Alpha-decay and be changed into206Pb.Therefore, in order to reduce alpha ray amount, it is also possible to think as impurity element In Pb or Bi, the content of any one or the content of Pb and Bi are also tried one's best low is preferred.
But, contained by Pb210Contained by Pb and Bi210Bi's is low containing ratio.Therefore, if Pb, The content of Bi is reduced to certain level, then it is believed that210Pb、210Bi is sufficiently removed to can be by α Quantity of X-rays X is reduced to the level of aforementioned range.On the other hand, in order to improve the sphericity of Cu ball 2, as front Described, the content of impurity element is higher to be preferred.Pb and Bi is all contained in Cu material as impurity element, Thus nucleus can be become during melted in the manufacturing process of Cu ball 2, it is possible to increase the sphericity of Cu ball 2. It is preferred, therefore, that with can be by210Pb and210Bi removes to alpha ray amount being reduced to aforementioned range The amount of level, containing any one or Pb and Bi in Pb or Bi.From this point of view, preferably It is that, in Cu ball 2, in Pb or Bi, the content of any one or the total content of Pb and Bi are more than 1ppm.
In Pb or Bi, the content of any one or the total content of Pb and Bi are more preferably more than 10ppm.On Limit value can reduce not restriction in the range of alpha ray amount, but from the sight of the electrical conductivity deterioration of suppression Cu ball 2 Point sets out, it is further preferred that the content of any one or the total content of Pb and Bi are less than in Pb or Bi 1000ppm.The content of Pb is more preferably the content of 10ppm～50ppm, Bi more preferably 10ppm～50ppm.
The sphericity of Cu ball: more than 0.95
The shape of Cu ball 2 is from the viewpoint of controlling solder joint height, and preferably sphericity is more than 0.95.Cu When the sphericity of ball 2 is less than 0.95, Cu ball becomes irregularly shaped, therefore forms height when forming projection Spend uneven projection, occur to engage bad probability and raise.Sphericity is more preferably more than 0.990. In the present invention, sphericity represents the gap with ball.Sphericity is such as by least square center method (LSC Method), Minimal regional center method (MZC method), maximum inscribe center method (MIC method), minimum outer hit The various methods such as heart method (MCC method) are obtained.Specifically, sphericity refers to: by 500 Cu balls 2 The arithmetic mean of instantaneous value that calculates when being respectively divided by major diameter of diameter, be worth closer to 1.00 expressions as the upper limit more Close to ball.The length of the major diameter in the present invention and the length of diameter refer to pass through Mitutoyo ULTRA Quick Vision, ULTRA QV350-PRO determinator that Corporation manufactures measure Length.
The diameter of Cu ball: 1～1000 μm
The diameter of Cu ball 2 is preferably 1～1000 μm.When being in this scope, it is possible to stably manufacture spherical Cu ball 2, furthermore it is possible to be connection short circuit during thin space between suppression terminal.
When illustrating the application examples of the Cu core ball 1 of the present invention, Cu core ball 1 can be used for soft solder powder The soldering paste that end, Cu core ball 1 and scaling powder are mixing.Here, the Cu core ball 1 of the present invention is for soldering paste Time, " Cu core ball " is referred to as " Cu core powder ".
" Cu core powder " is the aggregation that each Cu core ball 1 possesses Cu core ball 1 above-mentioned characteristic, multiple. Such as, with the single Cu core ball of the form compounding etc. with the powder in soldering paste in occupation mode Shang You district Not.Similarly, when the formation of solder projection, generally also process with the form of aggregation, therefore " the Cu core powder " that used by this way has any different with single Cu core ball." Cu core ball " is with quilt When being referred to as the form use of " Cu core powder ", generally, a diameter of 1～300 μm of Cu core ball.
Additionally, the Cu core ball 1 of the present invention can be used for being dispersed with the shaping solder of Cu core ball 1 in soft solder. In soldering paste and shaping solder, such as, use and consist of the soft of Sn-3Ag-0.5Cu (each numerical value is quality %) Brazing filler metal alloy.It should be noted that the present invention is not limited to this solder alloy.And then, the present invention Cu core ball 1 can be used for the soldered fitting of electronic unit.Additionally, it is contemplated that the present invention may be use with using Cu as The post (column) of core, pier (pillar), the form of granule.
One example of the manufacture method of the Cu core ball 1 of the present invention is illustrated.
Using being positioned over the plate i.e. refractory plate of ceramic such thermostability as the Cu material of material, with refractory plate Heat in stove together.Refractory plate is provided with the bottom groove for hemispherical multiple circles.The diameter of groove, The degree of depth suitably sets according to the particle diameter of Cu ball, the most a diameter of 0.8mm, and the degree of depth is 0.88mm.Additionally, The Cu material of the chip shape obtained cutting off Cu fine rule is (hereinafter referred to as " chip material ".) one by one Put in the groove of refractory plate.
For having put into the refractory plate of chip material in groove, heat up in the stove being filled with ammonolysis craft gas To 1100～1300 DEG C, carry out the heat treated of 30～60 minutes.In-furnace temperature now reaches the fusing point of Cu Time above, chip material is melted and becomes spherical.Then, making cooling in stove, Cu ball 2 is at refractory plate Groove internal shaping.After cooling, the Cu ball 2 of shaping at the temperature less than Cu fusing point that is 800～1000 DEG C again Carry out heat treated.
Additionally, as additive method, have following method: by the drop of melted Cu from being arranged at the bottom of crucible Dripping in the aperture in portion, makes this drop cool down, and Cu ball 2 carries out the atomization of pelletize；Utilize heat plasma Body, cuts METAL HEATING PROCESS to the method for 1000 DEG C of pelletizes carried out above by Cu.Such pelletize can be formed Cu ball 2 respectively at a temperature of 800～1000 DEG C implement 30～60 minutes reheating process.
In the manufacture method of the Cu core ball 1 of the present invention, it is also possible to will be as Cu ball 2 before to Cu ball 2 pelletize The Cu material of raw material at 800～1000 DEG C, carry out heat treated.
Cu material as the raw material of Cu ball 2, it is possible to use such as granule, line, pier etc..Never cross From the viewpoint of degree reduces the purity of Cu ball, the purity of Cu material can be 99.9～99.99%.
And then, when using highly purified Cu material, can be by same for the holding temperature of melted Cu Be reduced to about 1000 DEG C, and do not carry out aforementioned heat treated.So, aforementioned heat treated can root Suitably omit according to purity, the alpha ray amount of Cu material, change.Additionally, it is high to produce alpha ray amount When Cu ball, special-shaped Cu ball, it is also possible to these Cu balls are recycled as raw material, can be further Reduce alpha ray amount.
Additionally, as make above-mentioned make Cu ball 2, flow of the electrolyte come on Cu ball 2 formed solder The method of layer 3, has a following method etc.: the galvanoplastic such as known barrel plating；It is connected to plating groove Pump makes plating solution produce High Speed Turbulent in plating groove, utilizes the turbulent flow of plating solution to form plating on Cu ball 2 The method of film；Plating groove arranges oscillating plate, makes it vibrate with the frequency of regulation, thus plating solution is entered Row High Speed Turbulent stirs, and utilizes the turbulent flow of plating solution and the method that forms plating film on Cu ball 2.
By the plating Ni layer of thick for coverlay on the Cu ball of diameter 100 μm (unilateral) 2 μm and then at plating Ni Form the Sn-Cu soft solder plating film of 18 μm on layer and make the Cu core ball of diameter about 140 μm as one Example illustrates.
An embodiment of the invention containing Sn-Cu plating solution in the medium based on water containing sulfonic acid Class and belong to Sn and Cu of metal ingredient as essential component.
Metal ingredient is in the plating solution with Sn ion (Sn2+And/or Sn4+) and Cu ion (Cu+/Cu2+) Form exists.Plating solution is mixed by the plating mother solution that will be mainly made up of water and sulphonic acids and metallic compound And obtain, for the stability of metal ion, preferably comprise organic complexing agent.
As the metallic compound in plating solution, such as, can exemplify following material.
As the concrete example of Sn compound, can enumerate: methanesulfonic acid, ethyl sulfonic acid, 2-propane sulfonic acid, Pyrogentisinic Acid The pink salt of the organic sulfonic acids such as sulfonic acid, STANNOUS SULPHATE CRYSTALLINE, stannum oxide, nitric acid stannum, stannic chloride, Tin tetrabromide., iodate Stannum, phosphoric acid stannum, stannous pyrophosphate, tin acetate, formic acid stannum, citric acid stannum, gluconic acid stannum, tartaric acid The sub-Sn compound such as stannum, lactic acid stannum, succinic acid stannum, sulfamic acid stannum, boron stannic fluoride, silicon stannic fluoride. These Sn compounds can be used alone one or mix two or more use.
As Cu compound, can enumerate: the mantoquita of above-mentioned organic sulfonic acid, copper sulfate, copper oxide, nitric acid Copper, copper chloride, copper bromide, Copper diiodide, cupric phosphate, Copper pyrophosphate., copper acetate, Tubercuprose., Fructus Citri Limoniae Acid copper, copper gluconate, cupric tartrate, Cupric Lactate., succinic acid copper, sulfamic acid copper, boron copper fluoride, Silicon copper fluoride etc..These Cu compounds can be used alone one or mix two or more use.
Additionally, form thickness (unilateral) 18 μm on the Cu ball being coated with plating Ni layer of diameter 104 μm Sn-Cu soft solder plating film time, need the electricity of about 0.0101 coulomb.
About the compounding amount of each metal in plating solution, with Sn2+It is calculated as 0.05～2mol/L, is preferably 0.25～1mol/L, it is calculated as 0.002～0.02mol/L with Cu, is preferably 0.003～0.01mol/L.Here, That participate in plating is Sn2+, therefore the present invention adjusts Sn2+Amount.
It should be noted that according to Faraday's laws of electrolysis, utilize following formula (1) to estimate desired soft The amount of precipitation of solder coating, calculates electricity, makes electric current carry out plating solution in the way of reaching the electricity calculated Energising, while make Cu ball and flow of the electrolyte limit carry out plating.The capacity of plating groove can be according to Cu ball Determine with total input amount of plating solution.
W (g)=(I × t × M)/(Z × F) formula (1)
In formula (1), w is electrolysis amount of precipitation (g), and I is electric current (A), and t is conduction time (second), M is the atomic weight (being 118.71 in the case of Sn) of the element separated out, and Z is that quantivalence is (in the case of Sn For divalent), F is Faraday constant (96500 coulombs), and electricity Q (A second) represents with (I × t).
In the present invention, while make Cu ball and flow of the electrolyte limit carry out plating, the method for flowing is limited the most especially System.For example, it is possible to utilize the rotation of rotating cylinder to make Cu ball and flow of the electrolyte as barrel plating method.
After plating, in an atmosphere, N2Atmosphere is dried, obtains the Cu core ball of the present invention.
Embodiment
Hereinafter, the embodiment of the Cu core ball 1 of the present invention is illustrated, but the present invention is not limited to this A bit.
<drop strength and thermal cycling test>
Make: formed the Cu core ball of solder layer, soft by containing Ag by the solder alloy not containing Ag Brazing filler metal alloy formed the Cu core ball of solder layer, the solder ball formed by the solder alloy not containing Ag and The solder ball formed by the solder alloy containing Ag, tests as follows: measure for fall wait impact The drop strength test of intensity and measure the thermal cycle examination for the flexible intensity caused by thermal cycle Test.
As Cu core ball 1 as shown in Figure 1, in embodiment 1, make the Cu core ball 1 of a diameter of 300 μm. The Cu core ball 1 of embodiment 1 forms thickness with Ni on the Cu ball 2 of a diameter of 250 μm and is calculated as 2 μm with one side Barrier layer 4, and with Sn-Cu alloy formed solder layer 3.The composition of Sn-Cu alloy is set to Sn-0.7Cu, is set to 0.7% by the addition of the Cu in solder layer 3.
As comparative example, in comparative example 1, make the Cu core ball forming solder layer with Sn-Ag-Cu alloy. The composition of Sn-Ag-Cu alloy is set to Sn-1.0Ag-0.7Cu.In comparative example 2, with same as in Example 1 The Sn-Cu alloy of composition makes solder ball.In comparative example 3, with the Sn-Ag-Cu with comparative example 1 same composition Alloy makes solder ball.
For thermal cycling test, use previous embodiment and the Cu core ball of each comparative example and solder ball, by 15 Individual semiconductor packages structure base board (PKG) is bonded on a printed circuit board (PCB) (PCB), makes and evaluates Substrate.Printed circuit board (PCB) use implements the size of pre-solder flux process on the surface of Cu layer 174mm × 120mm, thickness are the Cu-OSP substrate of 0.8mm.Semiconductor packages structure base board uses size It it is the Cu-OSP substrate of 12 × 12mm.
Drop strength is tested, uses previous embodiment and the Cu core ball of each comparative example and solder ball, will 3 semiconductor packages structure base boards are bonded on a printed circuit board (PCB), make and evaluate substrate.Printed circuit Plate uses the size implementing the process of pre-solder flux on the surface of Cu layer to be 30 × 120mm, thickness is 0.8mm Cu-OSP substrate.Semiconductor packages structure base board uses Cu-OSP substrate.
On the semiconductor packages structure base board used in thermal cycling test and drop strength test, forming thickness is The protecting film of 15 μm, forms the peristome that opening diameter is 240 μm on protecting film, will with reflow soldering The Cu core ball of embodiment or comparative example or solder ball engage.As Reflow Soldering condition, thermal cycling test with Drop strength is tested all at N2Under atmosphere, peak temperature is set to 245 DEG C, at 140～160 DEG C, carries out 20 Second preheats, 220 DEG C of finally heating in 40 seconds carried out above.
So, the semiconductor packages structure base board being bonded to Cu core ball or solder ball is respectively arranged in thermal cycle The printed circuit board (PCB) of test and the printed circuit board (PCB) of drop strength test.For thermal cycling test and use When drop strength is tested, all by the soldering paste consisting of Sn-3.0Ag-0.5Cu of solder alloy with thickness It is that 100 μm, the mode of a diameter of 240 μm carry out printing on a printed circuit, utilizes the reflow soldering will The semiconductor packages structure base board of the Cu core ball or solder ball that are bonded to embodiment or comparative example is connected to print Printed circuit board.As Reflow Soldering condition, under air, peak temperature is set to 245 DEG C, at 140～160 DEG C Under carry out 70 seconds preheating, 220 DEG C of finally heating in 40 seconds carried out above.
In drop strength test, for made evaluation substrate, use special fixture that substrate two ends are solid It is scheduled on and is suspended in the position of 10mm above base.According to JEDEC standard, repeatedly apply acceleration 1500G Impact, initial resistivity value the moment rising 1.5 times is considered as fracture, record drop number.
Thermal cycling test utilizes series circuit for made evaluation substrate METHOD FOR CONTINUOUS DETERMINATION resistance.Use The thermal shock device TSA101LA that ESPEC CORP. manufactures, will at-40 DEG C and+125 DEG C successively Keep the process of 10 minutes as 1 circulation respectively, the resistance value moment more than 15 Ω is considered as fracture, note When all soft solder junction surfaces of 15 semiconductor packages structure base boards on record printed circuit board (PCB) are destroyed Heat exhaustion cycle-index.For every 1 composition, make 10 groups and evaluate substrate, carry out 10 tests, will Its meansigma methods is as result.
It is to implement the Cu-OSP substrate that pre-solder flux processes on the surface of Cu layer by semiconductor packages structure base board The result of the test of situation be shown in table 1.
[table 1]
Semiconductor packages structure base board is to implement the Cu-OSP substrate that pre-solder flux processes on the surface of Cu layer Time, as shown in table 1, for forming the Cu core ball of the embodiment 1 of solder layer with Sn-Cu alloy, fall strong Degree improves, and the intensity for thermal cycle also obtains exceeding the value of required 1500 time.
When semiconductor packages structure base board is Cu-OSP substrate, for forming solder layer with Sn-Ag-Cu alloy The Cu core ball of comparative example 1, drop strength obtains the intensity of regulation, but observe for thermal cycle strong The reduction of degree.
When semiconductor packages structure base board is Cu-OSP substrate, Sn-Cu alloy the weldering of the comparative example 2 formed In pellet, drop strength improves, but observes the reduction of the intensity for thermal cycle.By Sn-Ag-Cu In the solder ball of the comparative example 3 that alloy is formed, drop strength, intensity for thermal cycle all obtain required Value.
So, for the Cu core ball of embodiment 1, when coalesced object thing is Cu-OSP substrate, can be filled Point drop strength and for the intensity of thermal cycle.
Here, for the Cu core ball of embodiment 1, the addition of the Cu in making solder layer is more than 0.1% And less than 3.0% scope in carry out drop strength test, thermal cycling test, result drop strength, for The intensity of thermal cycle all obtains required above value.But, when to make the addition of Cu be about 3.0%, soft The fusing point of brazing filler metal alloy uprises.Therefore, Sn-Cu alloy the addition of the Cu in the solder layer formed is excellent Choosing is set to more than 0.1% and less than 2.0%.
<mensuration of alpha ray amount>
Then, make the Cu ball that sphericity is high, measure the Cu being formed with solder layer on the surface of this Cu ball The alpha ray amount of core ball.
The preparation of Cu ball
The preparation condition of the Cu ball that investigation sphericity is high.Prepare purity be 99.9% Cu granule, purity be The Cu line of less than 99.995% and the purity Cu plate more than 99.995%.Put into respectively in crucible, so After the temperature of crucible is warming up to 1200 DEG C, carry out 45 minutes heat treated, be certainly arranged at crucible bottom The drop of the melted Cu of aperture dropping, cools down drop, thus Cu ball is carried out pelletize.Thus it is prepared for putting down All particle diameters are the Cu ball of 250 μm.Elementary analysis result and the sphericity of prepared Cu ball are shown in table 3.
Sphericity
Hereinafter, the assay method of sphericity is described in detail.Sphericity utilizes CNC determining image system System measures.Device is ULTRA Quick Vision, ULTRA that Mitutoyo Corporation manufactures QV350-PRO。
Alpha ray amount
The assay method of alpha ray amount is as follows.The mensuration of alpha ray amount employs the α of gas flow proportional counter and penetrates Line determinator.Measuring sample is Cu ball to be paved with the plane shallow end container in 300mm × 300mm form 's.This mensuration sample is put into alpha ray determinator, placement 24 hours under PR-10 air-flow, then Measure alpha ray amount.
It should be noted that the PR-10 gas (argon 90%-methane 10%) used in Ce Dinging is by PR-10 Gas be filled in gas bomb after through the gas of more than 3 weeks.The gas bomb that use have passed through more than 3 weeks is In order to defer to JEDEC (EEE electronic equipment engineering joint committee (Joint Electron Device Engineering Council)) in the guide of alpha ray assay method of regulation make to enter into gas bomb Radon in air will not produce alpha ray.
Elementary analysis result, the alpha ray amount of prepared Cu ball are shown in table 2.
[table 2]
In the unit of the elementary analysis result of ※ alloy composition, only U, Th is quality ppb
The unit of other elements and total impurities amount is quality ppm
As shown in table 2, for employing the Cu line of Cu granule that purity is 99.9% and less than 99.995% Cu ball, sphericity is illustrated as more than 0.990.On the other hand, as shown in table 3, for employing purity The Cu ball of the Cu plate more than 99.995%, sphericity is less than 0.95.Therefore, embodiment described below and In comparative example, all use the Cu ball of the Cu line manufacture by less than 99.995% to prepare Cu core ball.
For the Cu ball manufactured by the Cu line of purity less than 99.995%, form Sn soft solder with following condition Plating film, the Cu core ball of preparation embodiment 2.
For the Cu core ball of embodiment 2, with coverlay on the Cu ball of diameter 250 μm thick (unilateral) it is The mode of the solder layer of 50 μm, is set to about 0.17 coulomb by electricity, uses following plating solution to carry out at plating Reason.By the cross section of the Cu core ball that SEM photograph observation covers with soft solder plating film, result thickness is about 50μm.After process, it is dried in an atmosphere, obtains Cu core ball.
Soft solder plating solution is made as follows: in stirring container, adds in 1/3 of the water needed for modulation plating solution Enter the aqueous methane sulfonic acid of 54 whole weight %, make base fluid.Then, the sulfur as chelating agent is added The one example i.e. acetylcysteine of alcoholic compound, after confirming its dissolving, adds the virtue as other chelating agent One example that is 2,2 '-dithiodianiline of fragrant race amino-compound.Formed thin azury gelatinous Methanesulfonic acid stannous it is rapidly added after liquid.Then, 2/3 of the water needed for addition plating solution, it is eventually adding surface One example of activating agent i.e. alpha-Naphthol polyoxyethylene ether (EO10 mole) 3g/L, the modulation of plating solution terminates.System The concentration having become the methanesulfonic acid in plating solution is 2.64mol/L, tin ion concentration is the plating solution of 0.337mol/L.
The methanesulfonic acid stannous used in this example is prepared from using following Sn sheet material as raw material.
About the elementary analysis of Sn sheet material of the raw material as soft solder plating solution and be formed at Cu core ball The elementary analysis of the soft solder plating film on surface, for U and Th, by high-frequency inductive coupling plasma body Mass spectrography (ICP-MS analysis) is carried out, and for other elements, passes through high-frequency inductive coupling plasma Body emission spectrometry (ICP-AES analysis) is carried out.For the alpha ray amount of Sn sheet material, except by Sn Sheet material is paved with outside the plane shallow end container of 300mm × 300mm, measures in the same manner as Cu ball.Cu core The alpha ray amount of ball measures in the same manner as aforementioned Cu ball.Additionally, for the sphericity of Cu core ball, also with It is measured under conditions of Cu ball is identical.These measurement results are shown in table 3.It should be noted that make For comparative example, determine the alpha ray amount of Sn sheet material.
[table 3]
In the unit of the elementary analysis result of ※ alloy composition, only U, Th is quality ppb
The unit of other elements and total impurities amount is quality ppm
According to table 3, in the stage of Sn sheet material, alpha ray amount has exceeded 0.2000cph/cm2, but should using Sn sheet material is formed in the embodiment 2 of solder layer with Sn-Cu alloy on Cu ball, and alpha ray amount is shown as low In 0.0010cph/cm2.Confirm that the Cu core ball of embodiment 2 is by utilizing plating method to form soft solder plating Film and make alpha ray amount reduce.
Even if additionally, the rising of alpha ray amount do not observed after making 2 years by the Cu core ball of embodiment 2 yet.
More than it should be noted that, the Cu core ball of the present invention is illustrated, but the shape of the present invention As long as can realize preventing from making the crushed such purpose of solder projection due to the deadweight of semiconductor package body, Just can be not limited to spherical, it is also possible to be applied to above-mentioned Cu stem stem.Specifically, it is also possible to application circle The upper and lower surface of the directly contact substrate such as post, triangular prism, quadrangular prism is by the cylinder more than 3 limits constituted.Become Cu post for core can be formed by known method, and the plating on the surface covering Cu post can also pass through The method used in above-mentioned Cu core ball forms coating layer.
Fig. 2 is the side cross-sectional, view of the schematic structure of the Cu stem stem illustrating present embodiment, and Fig. 3 is this reality Execute the top cross-sectional view of the schematic structure of the Cu stem stem of mode.The Cu stem stem 5 of present embodiment is by Cu post 6 are constituted with the solder layer 7 covering Cu post 6.
The diameter of the upper surface and bottom surface that constitute the Cu post 6 of the Cu stem stem 5 of the present invention is preferably 1～1000 μm, especially for thin space time be more preferably 1～300 μ, more preferably 1～200 μm, Most preferably 1～100 μm.And, the height L of Cu post 6 is preferably 1～3000 μm, especially for carefully 1～300 μ, more preferably 1～200 μm, most preferably 1～100 μm it are more preferably during spacing.Cu post The diameter of 6 and height L be when being above-mentioned scope, makes between terminal to be mounted for possibility for thin space, therefore can Enough suppression connect short circuit, and are capable of the miniaturization of semiconductor package body and highly integrated.
The purity of Cu post 6 of the Cu stem stem 5 of the composition present invention in addition to the size of above-mentioned Cu post 6, α Quantity of X-rays X, the impurity etc. contained optimum condition identical with the condition of the Cu ball 2 of the present invention.Need explanation , for Cu post 6, owing to not requiring sphericity, thus without purity be below 4N5, i.e. without miscellaneous The content of prime element is more than 50ppm.But, as long as can reduce in the range of alpha ray amount, with regard to nothing The content of impurity need to be reduced to the limit, if making the content of U and Th to reduce alpha ray amount is regulation Below value, then without making the content of any one or the content of Pb and Bi in Pb or Bi be reduced to the limit. Even if the content of impurity not being reduced to the limit, also drop strength and thermal cycling strength will not be produced shadow Ring.
Additionally, constitute soft solder composition, the alpha ray amount of the solder layer 7 of the Cu stem stem 5 of the present invention, contain The optimum condition of impurity etc. is identical with the condition of the solder layer 3 of the present invention.
And then, the optimum condition of the alpha ray amount etc. of the Cu stem stem 5 of the present invention and the Cu core ball 1 of the present invention Condition is identical.
For the Cu stem stem 5 of the present invention, barrier layer 8 can be formed between Cu post 6 and solder layer 7. Barrier layer 8 is made up of more than the a kind element selected from Ni or Co etc., prevents the Cu constituting Cu post 6 from diffusing to Solder layer 7.
The Cu stem stem 5 of the present invention can also be used for connecting the silicon of the electrode between the semiconductor chip of stacking Perforated electrodes (through-silicon via:TSV) uses.TSV manufactures as follows: by being etched in Perforate in silicon, sequentially forms insulating barrier in hole, is positioned at through conductor thereon, grinds the upper following table of silicon Face, makes through conductor expose in upper and lower surface, thus manufactures.In this operation, used in the past and passed through plating Method fills Cu etc. and the method that forms through conductor in hole, but in the method, due to by whole for silicon leaching Stain is in plating solution, therefore has the worry of the absorption of impurity, moisture absorption.Therefore, it can the Cu stem stem of the present invention 5 are directly inserted into the hole being formed in silicon and are used as through conductor along short transverse.Cu stem stem 5 is inserted into Time in silicon, can be engaged by solderable material such as soldering paste, during additionally, Cu stem stem 5 is inserted in silicon, Can also only engage with scaling powder.Thus, it is possible to prevent the bad of the absorption of impurity, moisture absorption etc., it is possible to To reduce manufacturing cost, manufacturing time by omission plating process.
The Cu stem stem 5 of the invention described above can obtain the drop strength above on an equal basis with solder post and for heat The intensity of circulation.

Claims (12)

1. a Cu core ball, it is characterised in that possess: by Cu or the Cu alloy containing more than 50% Cu The sandwich layer constituted；
It is made up of and covers the solder layer of described sandwich layer the solder alloy comprising Sn and Cu.
Cu core ball the most according to claim 1, it is characterised in that described solder layer contain 0.1% with Going up and the Cu of less than 3.0%, surplus is made up of Sn and impurity.
Cu core ball the most according to claim 2, it is characterised in that with comprising in Ni and Co The covered described sandwich layer of layer of more than a kind element is covered by described solder layer.
Cu core ball the most according to claim 3, it is characterised in that alpha ray amount is 0.0200cph/cm2 Below.
5. a soldering paste, it is characterised in that use the Cu core ball according to any one of claim 1～4.
6. one kind shapes solder, it is characterised in that use the Cu core according to any one of claim 1～4 Ball.
7. a soldered fitting, it is characterised in that use the Cu core according to any one of claim 1～4 Ball.
8. a Cu stem stem, it is characterised in that possess: by Cu or the Cu alloy containing more than 50% Cu The sandwich layer constituted；
It is made up of and covers the solder layer of described sandwich layer the solder alloy comprising Sn and Cu.
Cu stem stem the most according to claim 8, it is characterised in that described solder layer contain 0.1% with Going up and the Cu of less than 3.0%, surplus is made up of Sn and impurity.
Cu stem stem the most according to claim 9, it is characterised in that with comprising in Ni and Co The covered described sandwich layer of layer of more than a kind element covered by described solder layer.
11. Cu stem stems according to claim 10, it is characterised in that alpha ray amount is 0.0200cph/cm2Below.
12. 1 kinds of soldered fittings, it is characterised in that use the Cu according to any one of claim 8～11 Stem stem.
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